The dopants of bis(trifluoromethane) sulfonimide lithium (Li-TFSI) and 4-tert-butylpyridine (TBP) in spiro-OMeTAD are significantly important for achieving highly efficient perovskite solar cells (PSCs). However, the volatility of TBP and hygroscopicity of Li-TFSI would accelerate the degradation process of PSCs. Herein, we demonstrated that the use of 1,6-diazidohexane (N3) in spiro-OMeTAD can retard the evaporation of TBP and avoid aggregation/migration of lithium salt, leading to an enhanced conductivity/uniformity of spiro-OMeTAD layer. Additionally, N3 can minimize the TBP-PbI₂ complex formation to improve the stability at perovskite/hole transport layer interface. As a result, we achieved a champion device with a power conversion efficiency (PCE) of 22.7% under AM 1.5G illumination. The unencapsulated devices can maintain good stability under illumination conditions. These findings provide a new strategy for the designs of extrinsic dopants in spiro-OMeTAD to further advance the stability of PSCs.

螺-OMeTAD中的双（三氟甲烷）磺酰亚胺锂（Li-TFSI）和4-叔丁基吡啶（TBP）的掺杂剂对于实现高效钙钛矿太阳能电池（PSC）非常重要。然而，TBP的挥发性和Li-TFSI的吸湿性会加速PSCs的降解过程。在此，我们证明了在螺-OMeTAD 中使用 1,6-二叠氮己烷 (N3) 可以延缓 TBP 的蒸发并避免锂盐的聚集/迁移，从而提高螺-OMeTAD 层的电导率/均匀性。此外，N3 可以最小化 TBP-PbI ₂复杂的形成以提高钙钛矿/空穴传输层界面的稳定性。因此，我们在 AM 1.5G 照明下实现了功率转换效率 (PCE) 为 22.7% 的冠军器件。未封装的器件可以在光照条件下保持良好的稳定性。这些发现为螺-OMeTAD中外源掺杂剂的设计提供了一种新策略，以进一步提高PSC的稳定性。